CN112876513A - Complex for catalyzing 4-methyl-1-pentene polymerization with high activity and preparation method thereof - Google Patents
Complex for catalyzing 4-methyl-1-pentene polymerization with high activity and preparation method thereof Download PDFInfo
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- CN112876513A CN112876513A CN202110043682.4A CN202110043682A CN112876513A CN 112876513 A CN112876513 A CN 112876513A CN 202110043682 A CN202110043682 A CN 202110043682A CN 112876513 A CN112876513 A CN 112876513A
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- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 28
- 230000000694 effects Effects 0.000 title abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 58
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 37
- 229910000071 diazene Inorganic materials 0.000 claims description 37
- 229910052763 palladium Inorganic materials 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003446 ligand Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- YMAZWFQPRHQWTA-UHFFFAOYSA-N 4-methoxy-2,6-dipropylaniline Chemical compound CCCC1=CC(OC)=CC(CCC)=C1N YMAZWFQPRHQWTA-UHFFFAOYSA-N 0.000 claims description 5
- AFPRJLBZLPBTPZ-UHFFFAOYSA-N acenaphthoquinone Chemical compound C1=CC(C(C2=O)=O)=C3C2=CC=CC3=C1 AFPRJLBZLPBTPZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 229920000306 polymethylpentene Polymers 0.000 description 10
- 239000011116 polymethylpentene Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- 235000019502 Orange oil Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000010502 orange oil Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/006—Palladium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/14—Monomers containing five or more carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a complex for catalyzing 4-methyl-1-pentene polymerization with high activity and a preparation method thereof; the flexible group is introduced into the ortho position of the imine nitrogen atom aromatic ring of the complex, so that the flexible group provides dynamic steric hindrance in the catalytic polymerization process, the spatial environment of a Pd catalytic active center is further finely adjusted, the branching degree and the molecular weight of a polymer are regulated, and meanwhile, the electron-donating group is introduced into the para position of the imine nitrogen atom aromatic ring, so that the power supply performance of the metal active center is enhanced, the active metal center of the complex is stabilized, and the catalytic activity of the complex is improved.
Description
Technical Field
The invention belongs to the field of polyolefin preparation, and particularly relates to a complex for catalyzing 4-methyl-1-pentene polymerization with high activity and a preparation method thereof.
Background
Olefin polymers are excellent in processability, chemical resistance, electrical and mechanical properties, and the like, and therefore are processed into extrusion molded articles, injection molded articles, blow molded articles, films, sheets, and the like, and are used in various applications such as daily sundries, kitchen goods, packaging films, fibers such as nonwoven fabrics, home electric appliances, mechanical parts, electrical parts, automobile parts, and the like. In particular, olefin polymers containing 4-methyl-1-pentene are used in various fields such as medical instruments, heat-resistant electric wires, and heat-resistant food containers as resins having excellent transparency, air permeability, chemical resistance, and heat resistance.
The research on the high-activity catalyst for high-activity catalysis of 4-methyl-1-pentene mainly focuses on the metallocene high-activity catalyst and the non-metallocene high-activity catalyst of the early transition metal system. However, the metallocene high-activity catalyst or non-metallocene high-activity catalyst of the early transition metal system has high manufacturing cost, and the defects that the co-high-activity catalyst Methyl Aluminoxane (MAO) is expensive and has large dosage, an active center is easily inactivated by the action of a polar functional group, olefin and polar monomer cannot be catalyzed in high activity to be copolymerized, the shape and the particle size of the polymer are difficult to control, and the like exist generally. On the basis of less research on the nickel palladium diimine high-activity catalyst for catalyzing the polymerization of 4-methyl-1-pentene, the invention provides a complex for catalyzing the polymerization of 4-methyl-1-pentene with high activity and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a diimine palladium complex with an ortho-position substituted by a flexible group.
Another object of the present invention is to provide a process for producing the above diimine palladium complex.
Still another object of the present invention is to provide the use of the above diimine palladium complex in the polymerization of 4-methyl-1-pentene.
The above purpose of the invention is realized by the following technical scheme:
a diimine palladium complex of the formula (I):
when the diimine palladium complex high-activity catalyst is applied to 4-methyl-1-pentene polymerization, the reaction conditions are mild, and the polymerization reaction does not need to be carried out under the harsh anhydrous and anaerobic conditions; the flexible group is introduced into the ortho position of the imine nitrogen atom aromatic ring, so that the flexible group provides dynamic steric hindrance in the catalytic polymerization process, the space environment of a Pd catalytic active center is further finely adjusted, the branching degree and the molecular weight of the polymer are regulated, and meanwhile, the electron-donating group is introduced into the para position of the imine nitrogen atom aromatic ring, so that the power supply performance of the metal active center is enhanced, the catalytic active center of the catalyst is stabilized, and the catalytic activity of the catalyst is improved.
A preparation method of a diimine palladium complex comprises the following steps:
1. under the nitrogen atmosphere, trimethylaluminum is firstly used for activating 2, 6-dipropyl-4-methoxyaniline, and then the trimethylaluminum and acenaphthenequinone are subjected to a ketone-amine condensation reaction to generate a diimine ligand.
Wherein the molar ratio of the 2, 6-dipropyl-4-methoxyaniline to the trimethylaluminum to the acenaphthenequinone is 1:1: 2.4.
Wherein the solvent used in the reaction is toluene.
2. Under the conditions of nitrogen atmosphere and room temperature, dissolving diimine ligand and (COD) PdMeCl in an organic solvent, and stirring for reaction for a period of time to obtain diimine palladium complex.
Wherein the molar ratio of the diimine ligand to the (COD) PdMeCl is 1: 1.2.
Wherein the organic solvent is dichloromethane.
Wherein the reaction time is 12-18 hours.
The invention also provides the application of the diimine palladium complex serving as a high-activity catalyst in 4-methyl-1-pentene polymerization.
The synthesis reaction formula is as follows:
the diimine palladium complex serving as a high-activity catalyst for 4-methyl-1-pentene polymerization can be used for preparing poly (4-methyl-1-pentene) under the conditions that the polymerization time is 2-8 h, the polymerization temperature is 30 ℃ and the polymerization pressure is 0.2 atm.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) flexible groups are introduced into the ortho position of the aromatic ring of the imine nitrogen atom, so that dynamic steric hindrance is provided in the catalytic polymerization process, the space environment of the Pd catalytic active center is further finely adjusted, and the branching degree and the molecular weight of the polymer are regulated and controlled; meanwhile, electron-donating effect groups introduced at the para position of the imine nitrogen atom aromatic ring enhance the power supply of the metal active center, are beneficial to stabilizing the catalytic active center of the catalyst and improve the catalytic activity of the catalyst.
(3) The application of the diimine palladium complex in catalyzing 4-methyl-1-pentene polymerization is less in research, so that the novel diimine palladium complex is prepared and applied to 4-methyl-1-pentene polymerization to research the polymerization performance of the diimine palladium complex in a catalytic reaction.
Drawings
FIG. 1 is a single crystal structural diagram of a diimine palladium complex prepared in example 2 of this invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
The structural formula of the diimine palladium complex in each example is as follows:
in the following examples, the number average molecular weight of the poly (4-methyl-1-pentene) produced was measured by gel permeation chromatography.
Example 1
This example provides a diimine ligand, which is synthesized as follows.
Under the conditions of nitrogen atmosphere and room temperature, 20mL of toluene and 12mL of 2, 6-dipropyl-4-methoxyaniline (12mmol) are sequentially added into a 100mL bottle with a branch mouth, and then 12mL of trimethylaluminum (1.0M, 12mmol) is slowly added; raising the reaction temperature to 110 ℃, cooling the reaction temperature to room temperature after reacting for 2 hours, and then adding acenaphthenequinone (5 mmol); at the moment, the reaction system changes from colorless to deep red and emits a large amount of heat; continuing to react for 6 hours at 110 ℃, then cooling to 0 ℃, and stopping the reaction system by using 5% sodium hydroxide ice water solution; the organic phase was extracted with ethyl acetate and then with anhydrous MgSO4Drying, and spin-drying the solvent under reduced pressure to obtain an orange oil; the product was isolated by silica gel column eluting with a eluent (petroleum ether: ethyl acetate 15: 1); recrystallization from ethanol gave pale yellow crystals with a yield of 63.2%.
Example 2
This example provides a diimine palladium complex, which is synthesized as follows.
Under the protection of nitrogen, 20mL of diimine ligand (0.5mmol), (COD) PdMeCl (0.6mmol) and dichloromethane were added to a Schlenk flask with a branch mouth, and the mixture was stirred at room temperature for 12 hours, then the solvent was evaporated under reduced pressure at room temperature to about 5mL, and 20mL of n-hexane was added, whereby a large amount of precipitate was generated. Filtration through a G4 filter bulb and washing of the precipitate with 3X 10mL of n-hexane followed by vacuum drying gave the diimine palladium complex as a yellow solid in 73.4% yield.
Example 3
This example provides poly (4-methyl-1-pentene) which is prepared as follows.
The glassware and the stirring magnetrons used were dried in an oven (120 ℃ C.) and all polymerization experiments were carried out in the absence of water and oxygen. Under the condition of continuous vacuum pumping, baking a 250mL round-bottom flask with a branch mouth for more than 1h under an infrared lamp at the temperature of 150 ℃ to remove moisture and air completely; introducing nitrogen for replacement twice, and introducing nitrogen to normal pressure; the water bath was kept constant at 30 ℃ and a metered amount of chlorobenzene was added, dissolved with stirring and injected with 2M of the monomer and 10. mu. mol of diimine palladium complex in 2mL of dichloromethane. After 2h of polymerization the reaction was stopped and Et was used3Precipitating in methanol after SiH is terminated, dissolving the precipitated polymer in petroleum ether, separating with silica gel column, concentrating, precipitating in methanol, washing the obtained polymer with ethanol for three times, and vacuum drying to constant weight. 3.46g of poly (4-methyl-1-pentene) having a number-average molecular weight of 13670g mol-1The molecular weight distribution was 1.34 and the degree of branching was 163 branches/1000C.
Example 4
This example provides poly (4-methyl-1-pentene) which is prepared as follows.
The polymerization conditions were the same as in example 3, the reaction time being 4h instead of 2 h. To obtain 3.62g of poly (4-methyl-1-pentene) having a number average molecular weight of 13762g mol-1The molecular weight distribution was 1.41 and the degree of branching was 160 branches/1000C.
Example 5
This example provides poly (4-methyl-1-pentene) which is prepared as follows.
The polymerization conditions were the same as in example 3, the reaction time being 6h instead of 2 h. To obtain 3.79g of poly (4-methyl-1-pentene) having a number average molecular weight of 13114g mol-1The molecular weight distribution was 1.34 and the degree of branching was 155 branches/1000C.
Example 6
This example provides poly (4-methyl-1-pentene) which is prepared as follows.
The polymerization conditions were the same as in example 3, the reaction time being 8h instead of 2 h. To obtain 4.32g of poly (4-methyl-1-pentene) having a number average molecular weight of 13469g mol-1The molecular weight distribution was 1.42 and the degree of branching was 149 branches/1000C.
From examples 3 to 6, the diimine palladium complex prepared by the invention has a good effect in catalyzing 4-methyl-1-pentene polymerization with high activity. However, the research using 4-methyl-1-pentene as a homo-or comonomer mainly focuses on the metallocene high-activity catalyst and the non-metallocene high-activity catalyst of the pre-transition metal system, but the metallocene high-activity catalyst or the non-metallocene high-activity catalyst of the pre-transition metal system has high manufacturing cost, and the defects that the co-high activity catalyst Methylaluminoxane (MAO) is expensive and large in dosage, an active center is easily deactivated by the action of a polar functional group, olefin and polar monomer cannot be catalyzed in a high activity, the shape and the particle size of a polymer are difficult to control, and the like generally exist (for example, patent application No. 201310521144.7).
Claims (9)
1. A diimine palladium complex, wherein the diimine palladium complex has a structure represented by formula (I):
2. the process for preparing a diimine palladium complex (I) according to claim 1, which comprises the steps of:
(1) under the nitrogen atmosphere, trimethylaluminum is used for activating 2, 6-dipropyl-4-methoxyaniline, and then the trimethylaluminum and acenaphthenequinone are subjected to a ketone-amine condensation reaction to generate a diimine ligand;
(2) under the conditions of nitrogen atmosphere and room temperature, dissolving diimine ligand and (COD) PdMeCl in an organic solvent, and stirring for reaction for a period of time to obtain diimine palladium complex.
3. The process for preparing a diimine palladium complex (I) according to claim 2, which is characterized in that: in the step (1), the molar ratio of the 2, 6-dipropyl-4-methoxyaniline to the trimethylaluminum to the acenaphthenequinone is 1:1: 2.4.
4. The process for preparing a diimine palladium complex (I) according to claim 2, which is characterized in that: in step (1), the solvent used for the reaction is toluene.
5. The process for preparing a diimine palladium complex (I) according to claim 2, which is characterized in that: in step (2), the molar ratio of the diimine ligand to (COD) PdMeCl is 1: 1.2.
6. The process for preparing a diimine palladium complex (I) according to claim 2, which is characterized in that: in step (2), the organic solvent is dichloromethane.
7. The process for preparing a diimine palladium complex (I) according to claim 2, which is characterized in that: in the step (2), the reaction time is 12-18 hours.
8. Use of the diimine palladium complex (I) of claim 1 as a catalyst in the polymerization of 4-methyl-1-pentene.
9. The use according to claim 8, wherein the polymerization is carried out for a reaction time of 2 to 8 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113603611A (en) * | 2021-08-19 | 2021-11-05 | 黄山学院 | Asymmetric acenaphthenyl alpha-diimine ligand, palladium complex thereof, preparation and application of complex |
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2021
- 2021-01-13 CN CN202110043682.4A patent/CN112876513A/en not_active Withdrawn
Non-Patent Citations (1)
| Title |
|---|
| 刘小芳: "烷基铝引发α-二亚胺镍配合物催化4-甲基-1-戊烯聚合研究", 《万方学位论文数据库》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113603611A (en) * | 2021-08-19 | 2021-11-05 | 黄山学院 | Asymmetric acenaphthenyl alpha-diimine ligand, palladium complex thereof, preparation and application of complex |
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